Pyranthrone dye compositions and process for dyeing



Patented Nov. 27, 1951 PYRANTHRONE DYE COMP() SITIONS AN D PROCESS FORDYEING Jerry M. Mecca, Somerville, N..J assignor to. American Cyanamid Company. New. Yorin Y@ arcorporation of Maine ,No.Drawingl ApplicationNQvemhcr 30 13.49,.,

Serial. N0- 1303353'- (Cl. fle-34) 1s claims.

l This invention relates toan improved process o f dyeingw-ith pyranthrone and its halogenated derivativeslyr anthronek (C. I. 1096)k has the following formllll CanHn Oz ov l;

and it, and its dibromo derivative (C. I. 1098*) are Well known vat dyesr of golden-orange color. When these dyes are dyed by'ordinary vat dyeing processes, which involvea strong alkali, such as sodium hydroxide and. a, reducing agent. Such as sodiumthydrosulte, there is a loss in strength and brilliance, Whenthe dyeing operation is carriecl outA at high-temperatures. O n the other hand, high temperature dyeing presentssnh largepractical economic. advariiiiige that the pIOlQeItQS 0f these two. dyes.. for` dyeing et. high temperatures., eporoechinethat of boilineweter. has hampered their` economic exploitation.

High temperature dyeing usually improves dye penetration. and/or levelness.` particularly with such fabrics as nylon. The fast-dyeingwhich is possible at high temperatures alsoinakes various continuous and semifcontinuous processes possible.

Inreferring` toa-dye bathit should be understood that Weare considering the sitiintioria? the time thev dye. is axed to the fabric. In many processes the dyeetuif. is present in a dye bath, or vat;in,so1ution. in the form of the reduced leuco compound, andthesoods are introduced-into this bath;- Inother. processes, Such as. ior example. piementdyeing processes. which lend themselves to continuous and semi-continuous processes of the package dyeing variety,` the dyestuf may be originally incorporatedv loosely in the ber in the formof a pigment and, then reduced by the dye bathA which contains only they reduoins oohe'iiiientsand; the caustic eikeliwhioh is necessary. In suon a oase. thepdye bath et the ber inoludestne dyestufi. bili includes it. actually; ih position. in the ber. Throughout. tins; oase.. the term dye I bath will; be used to cover both typesof situan au tion.

This invention is based on the discovery that when certain nitrogen compounds areincorporatedinto the vat dye bath, improved strength and brightness are olotainablein high temperature dying with pyranthrones; such as pyranthrone and;oioiomooyrehihione- These nitrogen compounds; for themost par-t organic in nature, are characterized by thev fact Vthat they contain a nitrogen atom united With at f hydroxylamine, and as thesecompounds are readily obtainable at moderate cost, they present a deiinite economical advantage. Nitrobenzene isalmost as effective! andf its evenlowerI cost also makes it a desirable n iaterialA to use.

It not known how the nitrogen compounds operate vin nreyeniinsloes of Steheih ono brilliance in high temperature dyeingfwith pyranthrone.; and. eeoordineiy the'nreeehi invention is. not. intended ilo bemlimiied to, ohr theon/ of eoiion- In partielle?.v the-.phenomene which uhderlie the. oreeentihvelhtion ere-oilzihemol'e myeterious, because, as is described and claimedV in my. copending application Serial ivo. 130,355, led November, 30.11.9.49. nitrogen4 oomooonds exert o similar. action,Withlvetoyesinfis which are sensitive to. overrednoiion o? f ieeoihooeiiion oi hieh ternoerohireev the of these oyes Whieh easilyA deoornposeiiior over reoiiieeoi. it iePoS- .Sible that the niofosenvr compounds hier ooi es some hihdoi a reduction beffen In the oeee of hyronthlfone,t and its. heloseneiefi derivatives. however,v soon., explanation is not tenoble.. he.- oauee it is. a known ohereoterieiie of theee. dyes that they donot showany appearanceoifdecompostionfor over reductioninbathsup to the boiling point of water. In spite of. this well known stability ofthe. dyestnife. the nitrogen' compounds exert their beneficia action to e inerhed degree- It is obvious that factors other thanprevention of over` reduction orieooinoosiiionet high temper- It is an advantage of the present invention that the amount of the nitrogen compounds to be used is not critical. There is, of course, a lower limit, and it has been found that when the amount of the nitrogen compounds is less than one-quarter by weight of the content of actual dyestuif in the bath, the improvements are not sufficiently marked to be of practical value. Above this minimum, results improve for a while, with increasing amounts of nitrogen compounds, but soon reach the point at which greater amounts of nitrogen compounds do not give any improvement. This point is approximately 16 parts by weight of the nitrogen compounds to 1 of dye. However, for practical operation, the improvement obtained with much smaller amounts (for example, from l to 3 parts of the nitrogen compounds per part of dye) so closely approaches the maximum improvement obtainable, that larger amounts of nitrogen compounds do not produce suii'icient improvement to justify the additional cost. Even the upper limit of 16 parts of nitrogen compounds does not represent the maximum amount which can be used, without destroying the improvement in strength and brilliance, which is the purpose of the present invention. Even when 50 parts of nitrogen compounds to 1 part of dye are used, the improvements are still to be noted; but, of course, such enormous amounts of nitrogen compounds are only of theoretical interest.

Another advantage of the present invention is that the manipulative techniques of high temperature dyeing are not, in any way, changed by its use. Dyeing conditions remain the same, as do dyeing times; and the only change is that the shades obtained are stronger and brighter.

The optimum amount of nitrogen compounds to be used depends, to some extent, on the temperature of the dye bath and on the time dur-` ing which dyeing takesl place. In general, the lfaster the dyeing, the smaller the amount of nitrogen compounds which can be used to give results lso closely approximating the optimum results, as to make larger amounts of nitrogen compounds practically unnecessary. When dyeing time is longer, asis customary, additional amounts of hydrosulte are added to make up for hydrosulte oxidized by the air, or by other factors.

It is an advantage of the present invention that it may be applied in severalways. For example, vat dye baths canbe made up by adding all of the ingredients, that is, dye, alkali, reducing agent and nitrogen compounds, to produce a finished bath. Another method which has the practical advantage of making it unnecessary for the dyer to control closely the proportion of all ingredients going into the dye bath, is to blend with the dyestui a, suitable amount of nitrogen compounds to form a powder or a paste. This blend, which constitutes a new article of manufacture included within the scope of the present invention, may be sold. The dyer may then prepare his bath with the dyestui blend, the alkali and the reducing agent in any -convenient order.

The invention will 'be-illustrated in greater detail in conjunction with the following specic examples. Parts are by weight.

EXAMPLE 1 10 parts of cotton yarn was dyed in a bath containing about 0.09 part of the real dye having Color Index No. 1098, 3 parts of sodium hydroxide, 3 parts of sodium hydrosulte, 1.5 parts of nitropropane in 400 parts of water. The bath was heated for 5 minutes at about 200 F. during which time the vat dye was reduced, after which the cotton yarn was entered and dyed for 60 minutes at about 200 F. The dyed yarn was then removed, and the excess dye liquor extracted from the yarn. The remaining dye on the yarn was then oxidized for five minutes in the air at room temperature, after which it was immersed in an oxidizing solution consisting of 0.1% glacial acetic acid solution and 0.1% sodium peroxide volumes) for 10 minutes at F. The dyed yarn was then rinsed in warm water to remove the excess acid, soaped at the boil for l0 minutes in 0.1% soap and 0.1% soda. ash solution, rinsed and dried. The color was a bright orange and the yarn was dyed a full shade.

A second dyeing was made like the `above except the 1.5 parts of nitro-propane were omitted from the dye bath. The material dyed in this bath was dull, weak and yellow.

EXAMPLE 2 The procedure of the preceding example was repeated except the dye having Color Index No. 1096 and 1.5 parts of sodium hydrosulte were added after 5 minutes and another 1.5 parts were added after 2'0 minutes. The color value of the yarn dyed in this dye bath is a much stronger and brighter orange than that of the yarn dyed in the control sample in which no nitro-propane is present.

EXAMPLE 3 10 parts cotton yarn were dyed in a, bath containing 0.9 parts of the real dye having Color Index No. 1096, 3 parts of sodium hydroxide, 3 parts of sodium hydrosulte, 1.5 parts of para chloro ortho nitraniline in 400 parts of Water. The bath was reduced for 5 minutes at 95 C. `after which the cotton yarn was entered and dyed for 60 minutes at 95 C. The dyeing was bright orange and the yarn was dyed a full shade.

A second dyeing was made exactly as above except the 1.5 parts of para chloro ortho nitraniline were omitted from the dye bath. The cotton yarn dyed in this bath was a weaker shade of orange.

EXAMPLE 4 The procedure of the preceding example was repeated except the dye having Color Index No. 1098 and 1.5 parts of sodium lhydrosulte were added after 5 minutes and another 1.5 parts were added after 20 minutes. The color value of the yarn dyed in this dye bath is a much stronger and brighter orangethan that of the yarn dyed in the control sample in which no para chloro ortho nitraniline is present.

EXAMPLE 5 The procedure of Example 1 was repeated except the 1.5 parts of nitro-propane were replaced with 1.5 parts of hydroxylamine hydrochloride. Again the dyeing was a bright orange with a nice red shade as compared to the dull yellower -shade obtained in the control dyeing'.`

amasar The procedure` of: the., preceding exalllilfe.` was repeated exceptthe 1.5 parts of; hydmxylemne hydrochloride. were replaced with; 1.5 parts. ofV nitrobenzene potassium sulfonate.

example.

- EXAMPLE 7 The procedure* of the preceding example was repeated except the 1.5: parts ot nitrobenzene potassium sulfate were replaced with 1.5 parts of nitrobenzene and after. 15 minutes an additional 1.5 parts of sodium hydrosulte were added. The shade. of thisY dyeing` was. a nice strong orange showingv that decomposition4 had;

not occurredv as in the control sample.

EEiAMPPLliLSl The procedure of the precedingI example, was repeatedy except the 1.5 parts of; nitrobenzene were replaced with 1.5 parts. of para. nitroacetr.

EXAMPLE The procedurekof Example lwas repeated except thecompound H ON (SOaK)2.2H2O was used instead of the nitro-propaneof Example l. `This compound was prepared asl follows:

Preparation of HON(SO3K)2.2H2O

42.5 parts potassiumy nitrite (0.5 mole) and 50 parts potassium acetateV werey dissolved in 100 partsof ice Water. This wasplaced in a 3-neck ask ttedvvith a stirrer. 750 parts of nely chipped ice were added and the stirrer started. SO2 gas Was passed into this mixture until antexcessvvvas added, as indicated by the eiuent gas discoloring ay dilute potassium permanganate solution. The temperature was kept around 0"v C. during the reaction. The crystals ofk HON SO3K)2.2H2O were ltered with a Bchner funnel and4 the precipitate washed with four portions of ice Water, each amounting to 25 parts, to remove sulte and acetate, The precipitater was not dried, but storedy damp in a refrigerator. Reference: Rollesson and Oldershavv, J. Am. Chem. Soc. 54, 9 77 (1932). The yarn dyed in the presence of the HON(SO3K)2.2H2O was a brilliant. orange of excellent strength as compared to the dull and yellower shade of the control dyeing.

EXAMPLE 1l =toa separate dye beaker.

'IIhe resultsj were similar to those obtained inthe.. preceding 20. parts of: natural cotton. yarn were. pre-.vreewth. approximatelyv 1/2% solution of; ai., pine, oil soap, thek excessremoved byy squeezingl and thev yarn then enteredinto thek 400 parts. ofV reduced.

vat dye and dyed at.,160 F. for. 45 minutes. The dyed.. yarn was then removed and the excess dyeliquor. extractedfrom theyarn. The remaining dye on the yarnwas then. oxidized for 5. minutes inthe air at room temperature, after whichitwas=immersed in an.- oxidizing solution consisting of 0.1% sodium. peroxideand. 0.1%. glacial; acetic Lacidsolutionfor- 10 minutes at 1.40F. The. dyed yarn was then rinsed in warm water to remove the excess glacial acetic, soaped at the boil for 101 minutes in.0.l.%v soap and0,.1%` soda ashV solution, rinsed and. dried. A. controlv dyel bathwas prepared' exactly likeithe above except the nitro-propane was omitted. This was used; to make a control dyeing using thesame procedure as above. The yarn dyed in the bath containing the nitro-propane was strongerand brighter thanV the yarn dyed. inthe controlv dye; bath.

EXAMPLE 12 The procedure ofthe preceding example was repeated except the dyeing time wasA 1 hour and*A vminutes. The yarn dyed in the bath containing thenitro-propane showedf an even greater` increase in strength and brightnessof shadeas compared to the control dyeings than thatobtained in the preceding example.

The procedure of Example 1 was repeated except rayon was used'in place of thel cot-tony and the results were essentially the sameV as those obtainedin Example 1.

EXAMPLE le The procedure ofI the preceding example was repeated except linenV was used in place ofthe rayon, and the results were substantially the same as those obtained when the rayon was-used.

EXAMPLE 15 The procedure of the preceding example was repeated except nylon was used in place ofthe linen. Quite unexpectedly the nylon was dyed a bright, strong shade of unusually level appearance and not the dull yellow shade obtained when no nitro-propane was present in the dye bath.

EXAMPLE 16' The procedure of Example 1 was repeated except 0.025 part ofthe nitro-propane were used instead of the 1.5 parts of Example 1. Thevimprovement in shade and brightness of this dyeing was denite but was not as pronounced as that obtained in Example l.

EXAMPLE 17 The 4procedure of Example 1 Was repeated eX- cept the nitro-propanewas replaced with Nf-(Z- nitro-Z-methyl-propyl) sulfanilic acid. The dyeing -made from the bath containing the nitrogen compound was a bright, strong, reddish orange shade ascompared to a dull, yellower shadefo;` the control dyeing.

EX.AMPL'Ev 18 A dyeing waslmadeat a temperature of about 150? F.- (approximately 50 pounds pressure) on 2.5 parts of x 80 bleached unmercerized cot'- ton; in. the apparatus described inV U. Se P. 2,405,167, using a dye bath containingv 009 part offfrealzdye 'having Color Index. No. 109 8, 1. part of the nitrogen compound describedv in the preceding example, 5.0 parts of sodium hydroxide and 6 parts of sodium hydrosulte, the dyeing being carried out in a dye bath having 300 parts of liquor for 2 minutes. The bath was then flushed with water to the sewer, the dyeing removed, oxidized and nished as in Example 1. A good, strong, bright red shade of orange was obtained.

A control dyeing in which no N-(2-nitro-2- methyl-propyl) sulfanilic acid was present but otherwise made as above was a dull yellow shade.

u EXAMPLE 19 .The procedure of the preceding example was repeated except a piece of nylon was used instead- EXAMPLE 20 500 parts of No. 20s, 2-ply, natural cotton yarn in package form were wet out with 7,000 parts of a 1A,% solution of the surface-active anionic material which had been preheated to 190 F. This was then dyed in a dye bath containing 9 parts of real dye having Color Index No. 1098, 15 parts of a surface-active anionic material and 22.5 parts of N- 2-nitro-2-methyl-propyl) sulfanilic acid in 1,000 parts of water, making a total 4dye bath of 8,000 parts.

The dye dispersion was rst heated to 190 F. and then circulated through the wet-out package for 10 minutes, after which 200 parts of 30 B. sodium hydroxide, Which had been preheated to 190 F., were added to the dye bath and circulated for 5f minutes, after which 50 parts of solid sodium hydrosulte were added and circulated for 25 minutes. The spent dye bath was then flushed from the machine. The dye Was oxidized with 2% of 10U-volume hydrogen peroxide for 10 minutes at 140o F., after which the package was soaped, rinsed and dried. A bright reddish orange dyeing having excellent levelness was obtained.

A control dyeing was made in the same manner except the nitrogen compound was omitted from the dye bath. The package dyed in the control bath was an uneven, dull yellowish shade.

EXAMPLE 2l 900 parts of the real dye, having Color Index No. 1098, were ground and dry blended with 250 parts of N-(2-nitro-2-methyl-propyl) sulfanilic acid. Ten parts of cotton were dyed in a bath containing 0.115 part of this blend, 3 parts of sodium hydroxide, and 3 parts of sodium hydrosulte in 400 parts of water using the general method of Example 1. The resultant dyeing was stronger, redder and brighter than a control dyeing made from a bath containing the same amount of real dye, alkali and hydrosulte but omitting the N- 2-nitro-2-methyl-propyl) sulfanilic acid.

EXAMPLE 22 450 parts oi the real dye of the preceding example were ground and dry blended with '7,500 parts of p-nitro-acetanilide. r'en parts of cotton yarn were dyed in a bath containing 1.6 parts of this blend, 3 parts of sodium hydroxide and 3 parts of sodium hydrosulte in 400 parts of water using the general method-of the preceding example. 'I'he dyeing obtained from this dye bath was stronger 'and brighter than that obtained .from a controldye bath in which no p-nitro- .acetanlde .was present.

EXAMPLE 23 960 parts of the dye having Color Index No.

1096 andy 2,400 parts of HON SO3K 2-2H2O were ground and dry blended to give a homogeneous mixture. abath containing 0.85 part of this blend, 3 parts of sodium hydroxide, and 3 parts of sodium hy..

EXAMPLE 24 460 parts of a 20% Wet press cake containing 92 parts of the real dye used in Example 21 and 25 parts of hydroxylamine hydrochloride wereA stirred together and made up to 1,000 parts with Water. One part of this aqueous paste was substituted for the 0.115 part of dry blended material of Example 21, the dyeing being made as in Example 21. The dyeing made from the bath containing the hydroxylamine hydrochloride was stronger and brighter than that made from a control dye -bath in which no hydroxylamine hydrochloride was present.

EXAMPLE 25 462.5 parts of the 20% Wet press cake containing about 92.5 parts of the dye having Color lndex No. 1098 and 400 parts of nitro-benzene potassium sulfonate were stirred together and then made up to 1,000 parts with water. One part of this paste was substituted for the one part of the paste of the preceding example, the dyengs were made as in the preceding example, and the results were satisfactory.

EXAMPLE 26 The procedure of the preceding example was repeated except part of the water needed to bring the paste to 1,000 parts Was replaced with glycerine to give a glycerine content of 5%-l0% on the final weight. Dyeings made with pastes containing glycerine were quite satisfactory.

EXAMPLE 27 The procedure of the preceding example was repeated except the glycerine was replaced by ethylene glycol. Cotton yarn dyed With this paste is commercially satisfactory.

EXAMPLE 28 The procedure of the preceding example was repeated except the Wet press cake was dispersed with l0 parts of the sodium salt of di-sulo-dinaphthyl methane, the humectant then added and the paste made up to 1,000 parts. Cotton yarn dyed in a bath containing one part of this paste but otherwise dyed as in Example 25 gave satisfactory results.

I claim:

1. A method of vat dyeing brous material to which alkali metal salts of the leuco vat pyranthrone dye are substantive with a pyranthrone dye, Which comprises dyeing the material at high temperature approaching the boiling point of Water in a bath containing the dyestulr, strong alkali, reducing agent, and an amount of a nitrogen compound, in which a nitrogen is attached by at least one covalence bond to oxygen and by at least one covalence bond to an element other than oxygen or nitrogen, equal to at least onevquarter the weight of the real dyestui'.

Ten Yparts of rayon yarn were dyed in..

nitrogen compound is N-(2-nitro-2-methy1- propyl) sulfanilic acid.

3. A method according to claim 2 in which the dyestuff is pyranthrone.

4. A method according to claim 2 in which the dyestuf is dibromopyranthrone.

5. A method according to claim 1 in which the dyestuff is pyranthrone.

6. A method according to claim 1 in Which the dyestuif is dibromopyranthrone.

7. As a new article of manufacture a blend of a pyranthrone vat dyestuff With an amount of a nitrogen compound, in which a nitrogen is attached by at least one ccvalence bond to oxygen and by at least one covalence bond to an element other than oxygen or nitrogen, equal to at least one-quarter the Weight of the real dyestu.

8. An article of manufacture according to claim 7 in which the nitrogen compound is N-(Z-nitro- 2-xnethyl-propyl) sulfanilic acid.

9. An article of manufacture according to claim 8 in which the dyestuff is pyranthrone.

10. An article of manufacture according to claim 8 in which the dyestuff is dibromopyranthrone.

11. An article of manufacture according to claim 7 in which the dyestuff is pyranthrone.

12. An article of manufacture according to i0 claim 7 in which the dyestuff is dibromopyranthrone.

13. A method according to claim 1 in which the nitrogen compound is a nitroalkane.

14. A method according to claim 13 in which the nitroalkane is a nitropropane.

15. A method according to claim 1 in which the nitrogen compound is a hydroxylamine compound.

16. An article according to claim '7 in which the nitrogen compound is a nitroalkane.

17. An article according to claim 16 in which the nitroalkane is a nitropropane.

18. An article according to claim '7 in which the nitrogen compound is a hydroxylamine compound.

JERRY M. MECCO.

REFERENCES CTED The following references are of record in the fle of this patent:

UNITED STATES PATENTS Number Name Date 2,029,999 Grieshaber Feb. 4, 1936 2,146,646 Nusslein Feb. 7, 1939 2,383,393 Kienle Aug. 21, 1945 

1. A METHOD OF VAT DYEING FIBROUS MATERIAL TO WHICH ALKALI METAL SALTS OF THE LEUCO VAT PYRANTHRONE DYE ARE SUBSTANTIVE WITH A PYRANTHRONE DYE, WHICH COMPRISES DYEING THE MATERIAL AT HIGH TEMPERATURE APPROACHING THE BOILING POINT OF WATER IN A BATH CONTAINING THE DYESTUFF, STRONG ALKALI, REDUCING AGENT, AND AN AMOUNT OF NITRO-ROGEN COMPOUND, IN WHICH A NITROGEN IS ATTACHED BY AT LEAST ONE COVALENCE BOND TO OXYGEN AND BY AT LEAST ONE COVALENCE BOND TO AN ELEMENT OTHER THAN OXYGEN OR NITROGEN, EQUAL TO AT LEAST ONEQUARTER THE WEIGHT OF THE REAL DYESTUFF. 